JP2957480B2 - Shoe outsole - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a shoe outsole, and more particularly to a shoe outsole excellent in slip resistance and abrasion resistance.

[0002]

2. Description of the Related Art Among the performances required for an outsole of a shoe (that is, a portion of a shoe sole in direct contact with the ground), slip resistance and abrasion resistance are mentioned.

[0003] However, it is difficult to satisfy the anti-slip property and the abrasion resistance at the same time by one means, and in the prior art, the improvement of the anti-slip property (that is, the difficulty of slip) is mainly achieved by the pattern (design) of the outsole. The wear resistance has been improved mainly by devising the material.

[0004] In order to improve the slip resistance, it is common to increase the number of grooves in the pattern or to provide projections. In order to improve the wear resistance, the outsole is generally made of a hard material. I have been.

[0005]

However, when shoes are used only on a certain road surface, a desired pattern can be obtained by designing a suitable pattern. In some cases, such as tennis all-round shoes, the same shoes are used on completely different grounds, and improvement in slip resistance cannot be solved only by improving the pattern. For example, even on a soft ground such as soil, even if the pattern greatly contributes to the improvement of slip resistance, it is difficult to expect excellent slip resistance with the pattern on hard ground.

[0006] As described above, the improvement of the anti-slip property is not limited to simply devising a pattern provided on the outsole.
It is also necessary to consider materials. In addition, the use of a material with excellent wear resistance for the outsole can reduce the thickness of the outsole, and as a result, the overall weight of the shoe can be reduced. Is preferable.

[0007] Accordingly, an object of the present invention is to provide a shoe outsole excellent in slip resistance and abrasion resistance in consideration of materials.

[0008]

According to the present invention, as a result of various studies to solve the above-mentioned problems, the base rubber is constituted by a mixture of a specific solution-polymerized styrene-butadiene rubber and a butadiene rubber, and The present invention provides a shoe outsole excellent in slip resistance and abrasion resistance by containing hydrated silica in a specific ratio with respect to a rubber component containing rubber as a main component.

That is, the present invention provides a loss coefficient (tan δ) at a dynamic strain of 0.25% of a temperature dispersion curve of dynamic viscoelasticity at a frequency of 10 Hz measured at a temperature rise temperature of 2 ° C./min in the vulcanized product. The base rubber is composed of a mixture of a solution-polymerized styrene-butadiene rubber 60 to 85% by weight and a butadiene rubber 15 to 40% by weight having a peak of -10 ° C to -30 ° C. By forming the outsole with a vulcanized molded product of a rubber composition containing 55 to 70 parts by weight of hydrated silica with respect to 100 parts by weight of the rubber component to be used, the outsole has excellent anti-slip properties and abrasion resistance. It was done.

In the present invention, the reason why the outsole has excellent anti-slip properties and abrasion resistance is not always clear at present, but the above-mentioned specific solution-polymerized styrene-butadiene rubber is mainly composed of the anti-slip properties of the out sole. Butadiene rubber mainly contributes to the prevention of hardening and cracking at low temperature caused by the use of the solution-polymerized styrene-butadiene rubber, and hydrous silica mainly contributes to moderate reinforcement. This is considered to be due to the effect.

In the present invention, when measuring the loss coefficient (tan δ), the frequency is 10 Hz, and the temperature is -10 ° C. to -30 ° C.
The condition was chosen for the following reasons.

The deformation frequency of the shoe outsole can be measured by a viscoelasticity measuring device in a frequency range (up to 100 Hz).
It is considered that the frequency is higher than that. Then, when the practical condition of the shoe was confirmed by the frequency-temperature conversion rule in the polymer viscoelastic material, the above-mentioned frequency of 10 Hz and temperature-
This is because it has been found that the range of 10 ° C to -30 ° C has a close relationship with the slip resistance and abrasion resistance of the outsole of the shoe.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The solution-polymerized styrene-butadiene rubber used in the present invention has the above-mentioned loss factor (t).
an δ) is at -10 ° C. to −30 ° C., and if it satisfies this condition, it can contribute to the improvement of the slip resistance and abrasion resistance of the outsole. Although various types can be used, those having a vinyl content of 50% or less are preferable in consideration of the molding time. Further, those having no contamination are preferable. The solution-polymerized styrene-butadiene rubber having a loss coefficient (tan δ) peak at a temperature lower than −30 ° C. cannot sufficiently improve the slip resistance and abrasion resistance of the outsole, and has a loss coefficient (tan δ). The solution-polymerized styrene-butadiene rubber having a peak at a temperature higher than -10 ° C cannot sufficiently prevent curing and cracking at low temperatures even when blended (mixed) with butadiene rubber.

In the present invention, the loss coefficient (tan δ) of the solution-polymerized styrene-butadiene rubber was measured based on 100 parts by weight of the solution-polymerized styrene-butadiene rubber, 3 parts by weight of zinc white, 1 part by weight of stearic acid, and 1 part by weight of hydrous silica. 40 parts by weight, 2 parts by weight of sulfur and 1.5 parts by weight of an accelerator [1.0 parts by weight of an accelerator NS (N-tert-butyl-2-benzothiazyl-sulfenamide) and an accelerator D]
(Diphenyl guanidine) 0.5 parts by weight] was subjected to press vulcanization at 160 ° for 30 minutes to measure the dynamic viscoelastic properties of the vulcanizate at a rate of 2 ° C./min at 10 Hz. Then, a temperature dispersion curve is created and a dynamic strain of 0.25
% In which the loss coefficient (tan δ) was measured. In the present invention, the butadiene rubber mixed with the solution-polymerized styrene-butadiene rubber is cis-1,4.
Those having a content of 90% or more are preferred.

In the present invention, the solution-polymerized styrene-butadiene rubber constituting the base rubber is 60 to 85% by weight,
Butadiene rubber is 15 to 40 % by weight. When the amount of the solution-polymerized styrene-butadiene rubber is less than 60% by weight, the effect of improving the slip resistance and abrasion resistance is not sufficiently exhibited.
If the content is more than 5% by weight, the reduction of butadiene rubber causes the rubber to harden or crack at low temperatures. The ratio of the solution-polymerized styrene-butadiene rubber to the butadiene rubber is preferably 70 to 80% by weight for the solution-polymerized styrene-butadiene rubber, and 20 to 30% by weight for the butadiene rubber.

Conventionally, rubber or resin has been generally used as the base material of the outsole of shoes, and rubber has been generally used as the base material of the outsole of sports shoes. However, it is isoprene rubber, butadiene rubber, styrene-butadiene rubber, etc., which are used alone or as a mixture, but in many cases, isoprene rubber is used as an essential component because of workability and the like. .

As described above, rubber has conventionally been used as the base material of the outsole of shoes, but a mixture of solution-polymerized styrene-butadiene rubber and butadiene rubber has been used as the base rubber of the outsole. Never. Even when a solution-polymerized styrene-butadiene rubber is used, it may have a low glass transition point (Tg), that is, a low peak temperature of a loss coefficient (tan δ), and may be used in the solution polymerization used in the present invention. Like styrene-butadiene rubber, the loss factor (t
Those having a peak of anδ) have never been used.
This is because those having such a high peak temperature of the loss coefficient (tan δ) are cured at a low temperature.

In the present invention, 55 to 70 parts by weight of hydrated silica is contained with respect to 100 parts by weight of a rubber component mainly composed of a base rubber comprising a mixture of the solution-polymerized styrene-butadiene rubber and butadiene rubber. The reason for containing a large amount of hydrous silica in this way is to obtain an appropriate reinforcing effect. If the hydrous silica is less than 55 parts by weight based on 100 parts by weight of the rubber component, an appropriate reinforcing effect cannot be obtained, If the amount of hydrated silica is more than 70 parts by weight based on 100 parts by weight of the rubber component, the processability becomes poor.

In the present invention, the term "base rubber composed of a mixture of the specific solution-polymerized styrene-butadiene rubber and butadiene rubber" as the main component of the rubber component means that the entire rubber component is composed of the specific base rubber. This means that the rubber component may be constituted by including a rubber other than the specific base rubber as long as the characteristics of the specific base rubber are not impaired. However, the amount of rubber other than the specific base rubber is preferably 10% by weight or less in the entire rubber component.

Further, by adding the silane coupling agent, the reinforcing effect of the hydrated silica is more remarkably exhibited. The addition amount of the silane coupling agent is preferably from 1/12 to 1/5 of the weight of the hydrous silica. If the amount of the silane coupling agent is less than 1/12 of the weight of the hydrated silica, the effect of the addition of the silane coupling agent is not sufficiently exhibited, and the amount of the silane coupling agent is 1% of the weight of the hydrated silica. When the ratio is more than / 5, the effect is not improved with an increase in the added amount, and the cost is increased.

Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfene, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane and the like are preferably used.

In the present invention, the rubber composition for an outsole includes a compounding agent usually used for compounding a rubber for an outsole of a shoe, for example, zinc white, stearic acid, a plasticizer,
An antioxidant, an accelerator, sulfur and the like can be appropriately blended.

For example, zinc white is 1 to 10 parts by weight based on 100 parts by weight of the rubber component, and stearic acid is 100 parts by weight of the rubber component.
0.5 to 10 parts by weight relative to 100 parts by weight of the rubber component, 0.5 to 10 parts by weight of the plasticizer, 0 to 5 parts by weight of the antioxidant with respect to 100 parts by weight of the rubber component, and sulfur A suitable amount is 0.5 to 5 parts by weight based on 100 parts by weight of the rubber component, and about 0.5 to 3 parts by weight of the accelerator is suitable for 100 parts by weight of the rubber component. It will not be done.

FIG. 1 is a side view showing an example of a shoe using an outsole of the present invention (however, shoelaces are not shown). In the figure, reference numeral 1 denotes a shoe body, and 2 denotes an outsole. And 3 is a midsole.

As described above, the outsole 2 is a portion that directly contacts the ground of the shoe sole.
Is a vulcanized molded article of a rubber composition comprising a mixture of a specific solution-polymerized styrene-butadiene rubber and a butadiene rubber and comprising a specific proportion of hydrous silica. ), But the shoe body 1 and the midsole 3 may have a known configuration. Further, the midsole 3 is not always necessary, and the outsole 2 may be directly bonded to the shoe body 1.

If the entire outsole 2 is made of a vulcanized molded product of a rubber composition containing a mixture of the specific solution-polymerized styrene-butadiene and butadiene as a base rubber and containing hydrous silica, the outsole 2 has the following effects. Is most remarkably exhibited, but the effect can be obtained even if the rubber composition is partially formed of a vulcanized molded article of the rubber composition, for example, such as a toe portion and a ball portion of a thumb.

The outsole of the present invention is particularly suitable for use in sports shoes (eg, tennis shoes, running shoes, training shoes, etc.), spikeless shoes for golf, winter shoes, and the like. It is not limited to only.

[0028]

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.

Examples 1 to 6 and Comparative Examples 1 to 6 Outsole rubber compositions having the compositions shown in Tables 1 and 2 were prepared. The blending amounts in the table are parts by weight, and details shown by symbols and generic names in the table are shown after Table 2.

The obtained rubber composition was filled in a mold for an outsole and vulcanized at 160 ° C. for 30 minutes to produce an outsole. The JIS-A hardness of the obtained outsole was measured, and the friction coefficient and wear resistance were examined. Tables 1 and 2 show the results together with the composition of the rubber composition for outsole. However, in showing in the table, the coefficient of friction and the abrasion resistance of Comparative Example 6 corresponding to the conventional rubber composition were 10%.
The index is set to 0. The measurement of JIS-A hardness is based on J
It carried out by the method prescribed | regulated to IS-K-6301. The method of measuring the coefficient of friction and wear resistance is as follows.

Coefficient of friction: A tennis hard court material was prepared, an outsole was attached to the device shown in FIG. 2, a 10 kg weight 12 was placed on the outsole 11, and the outsole 11 was hard-coated in that state. 13 is measured. Travel speed is 500mm
/ Min, and the moving distance is 50 cm. The friction coefficient is indicated by an index with the friction coefficient of Comparative Example 6 being 100. The higher the index of the coefficient of friction, the better the slip resistance of the outsole and the less the outsole slips. In FIG. 2, reference numeral 14 denotes a load cell;
5 is a pulley, and 16 is a jig for attaching to a load cell.

Abrasion resistance: 20 mm thick from outsole
A test piece of 70 mm × 70 mm was sampled, attached to an apparatus as shown in FIG. 3, a load of 5 kg was applied, and the test piece 21 was placed on the hard coat material 22 at a speed of 500 mm / min for a distance of 1 m. Move repeatedly. Then, the weights before and after the test are measured to determine the weight loss. The indication of the abrasion resistance is also the weight after the test of Comparative Example 6 (that is,
(Residual amount) as 100. The larger the index, the better the wear resistance.

Further, the obtained outsole is adhered to a shoe main body portion (provided that the midsole is already adhered) with an adhesive to produce a tennis shoe, which is put on a monitor, and is put on a tennis court (hard court). A monitor test was conducted on the usability mainly due to the difficulty of sliding. The results are shown in Tables 1 and 2 together with the composition of the rubber composition for outsole. The method of this monitor test is as follows.

Monitor test: Ten monitors were put on tennis shoes using the outsole of Examples 1 to 6 and Comparative examples 1 to 6, and the feeling of use on a tennis court (hard court) was evaluated on a five-point scale. . The best value is indicated by 5 points and the worst value is indicated by 1 point. In this monitor test, the higher the evaluation point, the better the usability.

[0035]

[Table 1]

[0036]

[Table 2]

SOL · SBR (1): Loss coefficient (tan
SOL-SBR (2): Solution-polymerized styrene-butadiene rubber having a peak of δ) at −10 ° C. SOL · SBR (3): Loss of solution-polymerized styrene-butadiene rubber having a loss coefficient (tan δ) peak at −25 ° C. Solution-polymerized styrene-butadiene rubber having a coefficient (tan δ) peak at −35 ° C. SBR (4): emulsion-polymerized styrene-butadiene rubber,
Uses JSR1502 (trade name) manufactured by Nippon Synthetic Rubber Co. BR: Butadiene rubber, JSR B manufactured by Nippon Synthetic Rubber Co.
R-11 (trade name, cis-1,4 content 96%) is used IR: isoprene rubber, JSR I manufactured by Nippon Synthetic Rubber Co., Ltd.
R2200 (trade name) used Plasticizer: Diana Process Oil PW3 manufactured by Idemitsu Kosan Co., Ltd.
80 (trade name) Hydrous silica: use Nip Seal VN3 (trade name) manufactured by Nippon Silica Co., Ltd. Silane coupling agent: Si69 (trade name, bis (3-triethoxysilylpropyl) tetrasulfen) manufactured by Tegusa Accelerator: Uses Noxeller NS (trade name) manufactured by Ouchi Shinko Chemical Co., Ltd. Anti-aging agent: Nocrack 200 manufactured by Ouchi Shinko Chemical Co., Ltd.
Use (product name)

The above SOL. SBR loss factor (tan
δ), that is, the loss coefficient (tan δ) of the solution-polymerized styrene-butadiene rubber is 3 parts by weight of zinc white, 1 part by weight of stearic acid, and hydrated silica (Nipseal) based on 100 parts by weight of each solution-polymerized styrene-butadiene rubber. VN3 (trade name)] 40 parts by weight, sulfur 2 parts by weight and accelerator 1.5 parts by weight [Noxeller NS (trade name) 1 part by weight and Noxeller D (trade name, manufactured by Ouchi Shinko Chemical Co., Ltd.)]
5 parts by weight] of the rubber composition press-vulcanized at 160 ° C. for 30 minutes, and the vulcanizate was measured under the conditions of a temperature rising rate of 2 ° C./min and a frequency of 10 Hz as described above.

As is clear from the comparison between the characteristics of Examples 1 to 6 shown in Table 1 and the characteristics of Comparative Examples 1 to 6 shown in Table 2, Examples 1 to 6 have the friction coefficient and wear resistance. Was high, the anti-slip property and the abrasion resistance were excellent, and the evaluation points in the monitor test were high, and the usability was excellent.

That is, 60 to 85% by weight of a solution-polymerized styrene-butadiene rubber and a butadiene rubber 1 having a peak loss coefficient (tan δ) in the range of -10 ° C. to -30 ° C.
The base rubber is composed of 5 to 40% by weight, and hydrated silica is added to 55% of the rubber component 100 containing the base rubber as a main component.
Examples 1 to 6 in which the content was within the range of 70 parts by weight were excellent in the slip resistance and the wear resistance.

On the other hand, Comparative Example 1 using solution-polymerized styrene-butadiene rubber having a low loss coefficient (tan δ) peak of −35 ° C., Comparative Example 2 using isoprene rubber instead of butadiene rubber, and solution polymerization Comparative Example 3 in which the use ratio of the styrene-butadiene rubber is small has poor abrasion resistance as compared with Examples 1 to 6, and Comparative Example 4 in which isoprene rubber is used instead of butadiene rubber and the content of hydrous silica is small. Comparative Example 5 using an emulsion-polymerized styrene-butadiene rubber instead of the solution-polymerized styrene-butadiene rubber and Comparative Example 6 using an isoprene rubber instead of the solution-polymerized styrene-butadiene rubber had poor anti-slip properties. Abrasion was also bad.

[0042]

As described above, according to the present invention,
It is possible to provide a shoe outsole excellent in slip resistance and abrasion resistance.

[Brief description of the drawings]

FIG. 1 is a side view showing an example of a shoe using the outsole of the present invention.

FIG. 2 is a diagram showing an apparatus used for measuring a coefficient of friction.

FIG. 3 is a diagram showing an apparatus used for measuring wear resistance.

[Explanation of symbols]

 1 Shoe body 2 Outsole

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08K 13/02 3:36 5:54) (C08L 9/06 9:00) (58) Fields surveyed (Int.Cl. ⁶ , DB name) C08L 7/00-9/06 A43B 13 / 04,13 / 22 C08K 3 / 36,5 / 54

Claims (2)

(57) [Claims] The base rubber is composed of a mixture of 60 to 85% by weight of a solution-polymerized styrene-butadiene rubber and 15 to 40% by weight of a butadiene rubber. A peak of a loss coefficient (tan δ) at a dynamic strain of 0.25% of a temperature dispersion curve of dynamic viscoelasticity at a frequency of 10 Hz measured at a rate of 2 ° C./min exists at −10 ° C. to −30 ° C. And a vulcanized molded article of a rubber composition containing 55 to 70 parts by weight of hydrated silica with respect to 100 parts by weight of a rubber component containing the above base rubber as a main component. 2. The outsole of a shoe according to claim 1, wherein the rubber composition contains a silane coupling agent in an amount of 1/12 to 1/5 of the weight of the hydrated silica.